Computational Design of High-χ Block Oligomers for Accessing 1 nm Domains

Qile P. Chen, Leonel Barreda, Luis E. Oquendo, Marc A. Hillmyer, Timothy P. Lodge, J. Ilja Siepmann

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17 Scopus citations


Molecular dynamics simulations are used to design a series of high-χ block oligomers (HCBOs) that can self-assemble into a variety of mesophases with domain sizes as small as 1 nm. The exploration of these oligomers with various chain lengths, volume fractions, and chain architectures at multiple temperatures reveals the presence of ordered lamellae, perforated lamellae, and hexagonally packed cylinders. The achieved periods are as small as 3.0 and 2.1 nm for lamellae and cylinders, respectively, which correspond to polar domains of approximately 1 nm. Interestingly, the detailed phase behavior of these oligomers is distinct from that of either solvent-free surfactants or block polymers. The simulations reveal that the behavior of these HCBOs is a product of an interplay between both "surfactant factors" (headgroup interactions, chain flexibility, and interfacial curvature) and "block polymer factors" (χ, chain length N, and volume fraction f). This insight promotes the understanding of molecular features pivotal for mesophase formation at the sub-5 nm length scale, which facilitates the design of HCBOs tailored toward particular desired morphologies.

Original languageEnglish (US)
Pages (from-to)4351-4361
Number of pages11
JournalACS Nano
Issue number5
StatePublished - May 22 2018

Bibliographical note

Funding Information:
This work was supported by the National Science Foundation through the University of Minnesota MRSEC under award number DMR-1420013. Computer resources were provided through this NSF award and also by the Minnesota Supercomputing Institute at the University of Minnesota.

Publisher Copyright:
© 2018 American Chemical Society.


  • block polymer phase behavior
  • high-χ block polymer
  • molecular simulations computational design
  • solvent-free surfactant


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